Treatment of textile materials and product



United States Patent.

TREATMENT, or TEXTILE MATERIALQAND rnonucr,

This invention relates to the treatment of textile materials. More particularly, the'inven'tion relates-to =amethod" for treating textile materials tore'n'der' them crease resistant and shrink resistant. 1 1

Specifically, the invention provides a new and highly efiicient method for treating'textile materials torender 2 them crease and shrinkresistantwhich' compriscs "im'' pregnating the textile fabric with an aqueous solution=con-- taining'a mixture of a polyepoxide and a=polyaldehyde, and an acid-acting curing catalyst and 'then heating the impregnated'fabric to arelatively high'temperature for 21 short period. The invention further provides improved textile'fa'brics prepared by the aforedescribed process Many textile fabrics, such as those preparedfrom' rayon and cotton, have rather poor resilience, i. e, they"are= easily creased or wrinkled when crushed or otherwise; subjected to localized physical force. I'n'additionfmany of the fabrics have poor dimensional stability as -ex= emplified by'po'or resistance to shrinkage. *Inbrder to overcome these "shortcomings it has been common practice" to treat the fabric with materials, such urea- "or"melamine-formaldehyde resin" or glyoxalythat could be subsequently insolubili zed within the' fabric" fibers. While these materials give some of the desired properties, they still leave- -much to be desired as all around crease and shrink proof agents. .In some cases 40 these materials give 'good wrinkle resistancebut poor shrink resistance, and in other cases they give good shrinkresistance but poor Wrinklibsistance. In addition, many of these additives cause a permanent discoloration of the treated fabric. Others do not afiect the color of 5 the fabric initially but after the fabric has been bleached and ironed orhot-air dried, the fabric becomes charrd or discolored. Stillothersf weaken' the 'rabriqs, such -as rayon, so that they'have"low""teiisile strength Fi i-tfigkmore, manyoflhe'fabrics treatedwith'the ate als have a harsh feel and poor abrasionresistance.

It is an object of theinventioii, therefore, to provide a new method for treating textile materials. It is a further object to provide a process for preparing textile fabrics having a high degree of crease resistance and shrink resistance. It is a, further object to provide ahiethod for endowing fabrics with 'ahigh' degree--of both wrinkle resistance and shrink resistance without having any deleterious effect on other properties as tensile strength. It is affurt'her object to providearrie'thod for prep'arin'g crease and shrink resistant fabrics which'are non-chi e retentive, i. e., can"be'bleached'andironed'withou ing discoloration of the fabric. It is a'fur'therob ect-to provide a method for rendering textile fabricscreas'e "nd shrink resistant without giving" the fabrics a -h'arsh eel V and poor abrasion. Otherob'jects and advantagesof the invention'will be apparent 'from the following-detailed description thereof.

It has now been discovered that these and other objects maybe accomplished by; the-novel process of the invention which comprises impregnating the textile-fabric with an'a queous solultioircontaini'ri'ga "ice 2 and a polyaldehyde, and an acid-acting curing agent, andvthen heating the impregnated fabric to a relatively highf-temperature'for a'short period. It has been found that-fabrics treated inthis manner have unexpectedly high crease resistance as wellas shrink resistance and, in fact, higher--crease and shrink resistance than could be accomplished by-using the same amount of either of the compon'entsseparately. In addition, it has been found that'these properties are obtained with little if any loss of wotheri'desired' properties, such as tensile strength, which: loss generally accompanies the addition of the above-noted conventional crease-proofing agents. The fabrics treated with the above-described combination also have a softjfeel and good hand and excellent abrasion resistance. It has also been surprisingly found that the fabrics-treated with the above mixture have no ability to retain chlorine and the treated fabrics may be bleached or'otherwise, exposed to chlorine without danger of being discolored, charred or weakened during subsequent heat-treatment. Y r

. Oneof-the-agents employed in the treatment of the fabric: -according to' the process of the invention isa pol'yepoxide.- 'The expression polyepoxide refers to those materials-possessing a plurality of epoxy, i. e.,* t

,C- groups in the molecule. The polyepoxides may be. saturat'e'dfor unsaturated, aliphatic, cycloaliphatic, aromatic or heterocyclic and may befitsubsti't l ted if 'desired .with various' s'ubstituents, such as halogen 5 atoms, 'hydroxyl gro'lfips'g'ethei radicals and the-like. They may also be monomeric or polymeric.

For clarity,'many"of the polyether polyepoxides and particularly those of the-polymeric type will bedescribed. thr ughout the specificationa'nd claims in terms of anepbxy equivalency. The term epoxy equivalency as.

usedlierein a'sthe same meaning as described in U. S. 2,633,458 :1

"-If thepolyepoxide material consists of a single compound 'and=al1 ofthe'epoxy'groups are intact, the epoxy equiya 'ncy 'will be integers, su'ch as 2,3,4, and the like. However," in the case of polymeric-type polye'poxides many of the materials may contain some:of the monom'eric rnono'epoxides or have some of their epoxy-groups 'hydr ted or otherwise 'reacted and/or contain.- macromolecules ofsom'ewhat different molecular: weight so the epoxy"equivalenc'y may be quite low and contain fractional values: The polymeric material may, for example, have an epoxy equivalency of 1.5, 1'.8," 2.5, and the'like. ""Pol"'p'oxi'des to be used inthe process of the invention l"3 bis(2;3 epoxypropoxy)benzene, '4,4'-bis(2,3- "ropoxy) diphenyl ether, l,3 bis(2,3-epoxyproy) .r ctane, 1,4 bis(2,3-epoxypropoxy)cyclohexane,

i 4,4" bis(2 hydroxy-3,4-epoxy-butoxy)diphenyldimethylcan'fbe usedffor' this purpose include resorcinol, catechol,

hydroquinone, methyl iresorcinol, or polynuclear phenols,

such as 2,2-bis(4-hydroxyphenyl)butane, 4,4'-dihydroxybenzophenone, bis(4-hydroxyphenyl)ethane, and 1,5-dihydronaphthalene.

Still a further group of polyepoxides comprises the poly epoxy polyethers obtained by reacting, preferably in the presence of an acid-acting compound, such as bydrofluoric acid, one of the aforedescribed halogen-containing epoxides With a polyhydric alcohol, and subsequently treating the resulting product with an alkaline component. As used herein and in the claims, the expression polyhydric alcohol is meant to include those compounds having at least two free alcoholic OH groups and includes the polyhydric alcohols and their ethers and esters, hydroxy-aldehydes, hydroxyketones, halogenated polyhydric alcohols, and the like. Polyhydric alcohols that may be used for this purpose may be exemplified by glycerol, propylene glycol, ethylene glycol, diethylene glycol, butylene glycol, hexanetriol, sorbitol, mannitol, pentaerythritol, polyallyl alcohol, polyvinyl alcohol, inositol, trimethylolpropane, bis(4-hydroxycyclohexyl)dimethylrnethane, 1,4-dimethylolbenzene, 4, 4-dimethyloldiphenyl, dimethyloltoluenes, and the like. The polyhydric ether alcohols include, among others, diglycerol, triglycerol, dipentaerythritol, tripentaerythritol, dimethylolanisoles, beta-hydroxyethyl ethers of polyhydric alcohols, such as diethylene glycol, polyethylene glycols, bis(beta-hydroxyethyl ether) of hydroquinone, bis(beta-hydroxyethyl ether) of bisphenol, beta-hydroxyethyl ethers of glycerol, pentaerythritol, sorbitol, mannitol, etc., condensates of alkylene oxides, such as ethylene oxide, propylene oxide, butylene oxide, isobutylene oxide, glycidyl, epichlorohydrin, glycidyl ethers, etc., with polyhydric alcohols, such as the foregoing and with polyhydric thioethers, such as 2,2-dihydroxydiethyl sulfide, 2,2-3,3'-tetrahydroxy dipropyl sulfide, etc. The hydroxyaldehydes and ketones may be exemplified by dextrose, fructose, maltose, glyceraldehyde. The mercapto (thiol) alcohols may be exemplified by alphamonothioglycerol, alpha,alphadithioglycerol, etc. The polyhydric alcohol esters may be exemplified by monoglycerides, such as monostearin, monoesters of pentaerythritol and acetic acid, butyric acid, pentanoic acid, and the like. The halogenated polyhydric alcohols may be exemplified by the monochloride of pentaerythritol, monochloride of sorbitol, monochloride of mannitol, monochloride of glycerol, and the like.

A further group of the polyepoxides comprise the polyepoxy polyesters obtained by esterifying a polycarboxylic acid with an epoxy-containing alcohol, such as, for example, the diglycidyl esters of polycarboxylic acids as diglycidyl phthalate, diglycidyl maleate, diglycidyl adipate and the like.

Other polyepoxides include the polyepoxypolyhydroxy polyethers obtained by reacting, preferably in an alkaline medium, a polyhydric alcohol or polyhydric phenol with a polyepoxide, such as the reaction product of a glycidyl ether of a polyhydric phenol with the same or diiferent polyhydric phenol, the reaction product of glycerol and bis(2,3-epoxypropyl) ether, the reaction product of sorbitol and bis(2,3-epoxy-2-methylpropyl) ether, the reaction product of pentaerythritol and 1,2-epoxy-4,5- epoxypentane, and the reaction product of bis-phenol and bis(2,3-epoxy-2-methylpropyl) ether, the reaction product of resorcinol and bis(2,3-epoxypropyl) ether, and the reaction product of catechol and bis(2,3-epoxypropyl) ether.

A group of polymeric-type polyepoxides comprises the hydroxy-substituted polyepoxide polyethers obtained by reacting, preferably in an alkaline medium, a slight excess, e. g., Ste 3 mole excess, of a halogen-containing epoxide, such as epichlorohydrin, with any of the aforedescribed polyhydric phenols, such as resorcinol, catechol, 2,2-bis(4-hydroxyphenyl)propane, bis[4-(2'-hydroxynaphthyl)-2-Z-hydroxynaphthyl] methane, and the like.

Other polymeric polyepoxides include the polymers and copolymers of the allylic ether of epoxy-containing alcohols. When this type of monomer is polymerized in the substantial absence of alkaline or acidic catalysts, such as in the presence of heat, oxygen, peroxy compounds, actinic light, and the like, they undergo additional polymerization at the multiple bond leaving the epoxy group unaffected. These allylic ethers may be polymerized with themselves or with other ethylenically unsaturated monomers, such as styrene, vinyl acetate, methacrylonitrile, acrylonitrile, vinyl chloride, vinylidene chloride, methyl acrylate, methyl methacrylate, diallyl phthalate, vinyl allyl phthalate, divinyl adipate, 2-chloroallyl acetate, and vinyl methallyl pimelate. Illustrative examples of these polymers include poly(allyl 2,3-epoxypropyl ether), allyl 2,3-epoxypropyl ether-styrene copolymer, methallyl 3,4-epoxybutyl ether-allyl benzoate copolymer, poly(vinyl-2,3-epoxypropyl)ether and an allyl glycidyl ether-vinyl acetate copolymer.

Coming under special consideration are the polyglycidyl polyethers of polyhydric alcohols obtained by reacting the polyhydric alcohol With epichlorohydrin, preferably in the presence of 0.1% to 5% by weight of an acid-acting compound, such as boron trifluoride, hydrofluoric acid, stannic chloride or stannic acid. This reaction is effected at about 50 C. to 125 C. with the proportions of reactants being such that there is about one mole of epichlorohydrin for every equivalent of hydroxyl group in the polyhydric alcohol. The result-' ing chlorohydrin ether is then dehydrochlorinated by heating at about 50 C. to 125 C. with a small, e. g., 10% stoichiometrical excess of a base such as sodium aluminate.

The products obtained by the method shown in the preceding paragraph may be described as polyether polyepoxide reaction products which in general contain at least three non-cyclic ether (-O) linkages, terminal epoXide-containing ether i in which R is the residue of the polyhydric alcohol which may contain unreacted hydroxyl groups, X indicates one or more of'the epoxy ether groups attached to the alcohol residue, y may be one or may vary in different reaction products of the reaction mixture from zero to more than one, and Z is one or more, and X+Z, in the case of products derived from polyhydric alcohols containing three or more hydroxyl groups, averages around two or more so that the reaction product contains on the average two or more than two terminal epoxide groups per molecule.

The preparation of one of these preferred polyglycidyl ethers of polyhydric alcohols may be illustrated by the following example showing the preparation of a glycidyl polyether of glycerol.

; t .R BA= AT.IQ .oF- crclnrnronrn'rners OF POLYHYDRIC Polyether A About 276 parts (3,moles) ;of.g lycer.ol.wastmixed with 83,2 parts (.9 moles). of epichlorohydrin. To this reaction mixture was. added parts, of. .diet-hyl .ether solution conta ining.about-.4.S% borontrifluoride. Thetemperature of this mixture was between 50 C. and 75 C. fonabout 3.hours. About .37.0. parts of the resulting glycerol-epichlorohydrin condensate was dissolved-in 900 parts of dioxane containing ,ab out 300. parts of sodium aluminate.

While agitating, the reaction mixture was :heated and refiuxed .at 93 C. for 9 hours. After-cooling to1 atmospheric temperature, .the insoluble material wasfiltred from the reaction-mixture and lowboiling substances rernoved by distillation to a temperature of about 150 C. at. 2O.mm. pr,essure. .Thepolyglycidyl ether, in-amount of .261 parts wasa pale ,yellow viscous-liquid. It ha d .an

Polyether :B

10.5 moles of ethylene oxide wasbubbledjthrough 35 moles glycerine containing an acid catalyst at 4050C. The resultingpro'duct' had'a molecular vweight ofj224 and a hydroxyl .value of 1.417 eq./ 100g. 101 parts of this ethylene oxide glycerine condensate Was placed in a reaction kettleand'heated to 6570. C. 'jSuflicientBFs- 'Ethylc'ther complex was added to bring-the pH to about 1.0 and then 132 parts of epichlorohydrin.added'dropwise. After all the epi had been added, the reaction was continuedfor about minutes .to assure completer reaction. This product was then dissolved in benzene and'57 parts of sodium. hydroxide were added in 7 equalport-ions at about 87-89 C(over a period of hour and thenfiltered to remove the salt. "The solvent and light ends. were then removed by stripping at a l-owvacuum. The resulting product had .a molecularweight of 455, and an epoxy value of .524-eq./ 100 g. For convenience,,this polyether will be referred to herein as Polyether B.

Polyether C One equivalent of 1,2,6 -hexanetriol was placed in a reaction kettle and heated to '6570 C. Suflioient BFs-Ethyl ether complex was added to bring the pH to about 1.0 and then 1 equivalent of epic'hl-orohydrin added d-rop w-ise. After all the epi had been added, the reaction was'continued'for about 15 minutes to assure complete reaction.

This product was then dissolved in acetone and sodium orthosilica-te was added at about 65 C. over a period of 0.5 hour and then filtered to remove the salt. The solvent and light ends were then removed by stripping at a low vacuum. The resulting product had a molecular weight of 325 and an epoxy value of .600 eq./100 g. for convenience, this polyether will be referred to herein as Polyether C.

Particularly preferred members of this group comprise the glycidyl polyethers of aliphatic polyhydric alcohols containing from 2 to 10 carbon atoms and having from 2 to 6 hydroxyl groups and more preferably the alkane polyols containing from 2 to 8 carbon atoms and having from 2 to 6 hydroxyl groups. Such products P eferably have an epoxy equivalency greater than 1.0, and still more preferably between 1.1 and 4 and a molecular weight between 300 and 1000.

Also of importance are the monomeric ,andpolymeric glycidyl polyethers of dihydric phenols obtained by reacting epichlorohydrin with a dihydric phenol in an alkaline medium. The monomeric products of this type may be represented by the general formula ally, b lasi les mpl lecul ut i -beaQQHiPIQ mixture of glycidyl polyethers of the generalformulai C/H2\C BPGH- 0- (R.- O-CHa-CH O H-CHa-O) 1r R-O-CHz- O/H-'\C\H whereinR is'a .divalenthydrocarbon radical of thedihyd-ric phenol and n is an integer of the series 0, 1,2, *3, etc. While-for-anysingle molecule of thepolyether n, is an integer, the factthat the'obtained polyether is a mixture of compounds cau'sesthedetermined value ofn to be-anaverage which is not necessarily zero or a whole number. The polyethers may, in .some cases, contain a very small amount of material with one or bOthjOfjhE terminal glycidyl radicals in hydrated form.

Theaforedescribed preferred glycidylpolyethers of the dihydric phenols may be prepared by reacting therequired proportions of t he dihydric phenol and the epichloro- "hydrin in-an alkaline-medium. The desired alkalinity is obtained by adding basic substances,-such as sodium or 'potassiumhydroxide, preferably in s'toichiometric excess to theepichlorohydrin. The reaction is preferably accomplished at temperatures withinthe range of from 50 C. to 150 C. 'T-he heating is continued for several hours to effecbthereaction and the product is then washed free of salt and base.

The preparation of some of the glycidyl'polyethers of the'dihydric-phenolswill be illustrated below.

"PREPARATION- OF GLYCIDYL" POLYETHERS OF DIHYDRIC PHENOLS Polyether D About Z -moles of'bis-phenol was dissolved in10 moles of epichlorohydrin and 1% to 2% water added to the resulting mixture. The mixture was then brought .to C. and 4 moles of solid sodium hydroxide. added in small portions over a period of about 1 hour. During the addition,,the temperature of the mixture vwas .held at about. C. to 110 C. After the sodium hydroxide had been added, the waterformed in the reactionand most of the epichlorohydrin was, distilled off. The residue that remained was combined with an approximately equal amount of benzene andthe mixture filtered to remove the .salt. The benzenewas then:removed to. yielda viscous liquid having a viscosity of about 150.poises at 25 C. anda molecular weight of about 350 (measured ebullioscopically in ethylene dichloride). The product .had an epoxy value of 0.50 eq./ g., and an epoxy. equivalency of 1.75. For convenience, this product will be referred to hereinafter as Polyether D.

Particularly preferred membersv of the above-described group are the glycidyl polyethers of the dihydric phenols, and especially 2,2-bis(4'-hydroxyphenyl) propane, having an epoxy equivalency between 1.1 and 2.0 and a molecular weight between 300 and900. :Particularly preferred are those having a Durrans Mercury Method softening point below about 60 C.

The glycidyl polyethers of polyhydric phenols obtained by condensing the polyhydricphenols with epichlorohydrin are also referredto as ethoxylene resins. See Chemical Week,.vol. 69, page27, for September 8, 1951.

Of particular value in the process oftheinvention are the polyepoxides containing only carbon, hydrogen, oxygen. and halogen atoms.

The polyaldehydes to be used in combination with the above-described .polyepoxides comprise those organic materials possessing a plurality of aldehyde, i. e.,

--C=O groups C These materials may be saturated or unsaturated, aliphatic, cycloaliphatic-aromatic or heterocyclic andsub- .stituted-with substituents,;such as alkoxy.radicals,-halogen atoms, ester radicals ,and the like. Examples pf I these polyaldehydes include,

' ma-ethyl-delta-isopropyl-adipaldehyde,

among others, glyoxal, glutaraldehyde, adipaldehyde, pimelaldehyde, suberaldehyde, glutaconaldehyde, alphahydroxyadipaldehyde, betamethoxyadipaldehyde, alpha,gamma dimethyl al pha- (methoxymethyl) glutaraldehyde, beta-allyloxy-pimelaldehyde, 1,4-cyclohexandicarboxaldehyde, 3-cyclohexene- 1,5 dicarboxaldehyde, 1,1,5 pentanetricarboxaldehyde and l,3,6-ctane-tricarboxaldehyde.

A prefered group of polyaldehydes comprise glyoxal, succinaldchyde, glutaraldehyde and hydrocarbyl-substituted glutaraldehydes, such as those of the formula wherein each R is hydrogen or an alkyl, cycloalkyl, alkenyl, cycloalkenyl, aryl, alkaryl or an aralkyl group. Examples of these dialdehydes include beta-methylglutaraldehyde, beta-gamma-dibutylglutaraldehyde, betaphenylglutaraldehyde, beta,gamma dibenzylglutaraldehyde, beta,gamma-dicyclohexylglutaraldehyde, and betaisopropylphenylglutaraldehyde. A detailed description of how to prepare these glutaraldehydes may be found in Smith et al., U. S. 2,546,018.

Another preferred group of polyaldehydes comprise the ether-substituted dialdehydes, such as those obtained by reacting a suitable alpha-methylene monoaldehyde, such as methacrolein, with an alcohol under controlled conditions and in the presence of a basic condensation catalyst. The over-all reaction which is effected in the execution of this process may be exemplified by the following equation:

oxymethyl) glutaraldehyde, and alpha,garnma-dioctylalpha-(octadecenyloxymethyl) glutaraldehyde. Especially preferred members of this group are those of the wherein R is a hydrocarbon or hydroxy-substituted hydrocarbon radical, and particularly an alkyl, alkenyl, cycloalkyl or cycloalkenyl radical and their hydroxysubstituted derivatives, and R1 is an alkyl, alkenyl cycloalkyl or cycloalkenyl radical, wherein 11 of the foregoing radicals preferably contain no more than 8 carbon atoms.

' A detailed description of the method for preparing the above-described preferred polyaldehydes may be found in copending patent application of Smith and Norton, Serial No.. 16,617, filed March 23, 1948.

Another preferred group of polyaldehydes comprise the 'hydroxy-substituted dialdehydes and particularly the alpha-hydroxy-substituted adipaldehydes, such as, for example, alpha-hydroxy-adipaldehyde, alpha-hydroxygamma, delta-dimethyladipaldehyde, alpha-hydroxy-gamand alpha-hydroxy-gamma-delta-dioctyladipaldehyde. A detailed description for preparing some of-these polyaldehydes from substituted dihydro-1,4-pyrans may be found in Whetstone et al.--U. S. 2,639,297.

Another group of preferred polyaldehydes comprise those obtained by condensation of methacrolein in the presence of aqueous alkali as described in I. Am. Chem. Soc. 60, 1737 and 1911 (1938), and polyaldehydes obtained by condensing acrolein with alcohols in the presence of a basic catalyst as described in German Patent 554,949.

Still another group of preferred polyaldehydes comprise the polymers and copolymers obtained by polymerizing unsaturated aldehydes. Examples of such unsaturated aldehydes include, among others, acrolein, alpha-methyl acrolein, alpha-ethyl acrolein, alpha-propyl acrolein, alpha-isobutyl acrolein, alpha-n-amyl acrolein, alpha-nhexyl acrolein, alpha-bromo acrolein, crotonaldehyde, alpha-chloro-crotonaldehyde, alpha-bromo-crotonaldehyde, alpha-beta-dimethylacrolein, alpha-methyl-betaethyl acrolein, alpha-ethyl-beta-propylacrolein, and the like. Preferred unsaturated aldehydes to be used in preparing these polymers include the alpha,beta-ethylenically unsaturated aldehydes, and particularly the 2-alkenals containing no more than 8 carbon atoms.

Monomers that can be copolymerized with the above described unsaturated aldehydes to form polyaldehydes comprise those compounds containing a polymerizable unsaturated linkage, and preferably a single CH2=C= group, such as, for example, styrene, alpha-methyl styrene, vinyl chloride, vinylidene chloride, methyl methacrylate, ethyl acrylate, acrylonitrile, methacrylonitrile, allyl acetate, vinyl acetate, chloroallyl caproate, allyl alcohol, isobutylene, allyl glycidyl ether, vinyl methyl ether, allyl glycolate, methyl allyloxy-acetate, vinyl pyridine, glycidyl methacrylate, hydroxyethyl methacrylate, octyl acrylate, vinyl pyrollidone, allyl dimethyl cyanurate, allyl butyl phthalate, dialkyl maleates, and the like. In preparing copolymers of the unsaturated aldehydes with these dissimilar monomers it is preferred to employ the dissimilar monomer in amounts varying from 1% to by weight of the total monomer mixture.

The ratio in which the polyepoxide and the polyaldehyde are combined in the mixture may vary within certain limits. At least 15% by weight and preferably from 15 to by Weight of the mixture should be made up of the polyepoxide and the remainder being the polyaldehyde. The highest wrinkle resistance and shrink resistance, however, are generally obtained when the polyepoxide varies from 30% to 70% by weight and the remainder being the polyaldehyde.

The polyepoxide and the polyaldehyde are applied to the fabric in the form of an aqueous solution. Many of the polyaldehydes and polyepoxides will be water soluble and the aqueous solutions may be prepared by merely adding the mixture of polyaldehyde and polyepoxide to the water. In other cases, it may be helpful to add solvents, such as acetone, ethyl alcohol and dioxane to the water, or to employ emulsifyinng agents to assist in the formation of the water solution. If emulsifying agents are employed, they are preferably those that are free of nitrogen and strong acidic groups, such as the monooleate of sorbitan polyoxyethylene, the trioleate of sorbitan polyoxyethylene, sorbitan tristearate, sorbitan monolaurate, polyoxyethylene esters of alkylphenols, carboxymethylcellulose, starch, gum arabic, polyvinyl alcohol, aryl and alkylated aryl sulfonates, such as cetyl sulfonate, oleyl sulfonate, sulfonated mineral oils, copolymers of vinyl methyl ether, maleic anhydride and the like, and mixtures thereof. The emulsifying agents are generally employed in amounts varying from 0.1% to 10% by weight and more preferably from 1% to 5% by Weight.

The amount of the mixture of polyepoxide and polyaldehyde to be employed in the impregnating solution will vary depending chiefly on the amount of the mixture to be deposited on the fabric and this in turn will depend upon the number of applications and the pick-up allowed mammal per application. -As indicated -hereina'fter, the :amount of the mixture to he applied to the -fabric -wlll generally vary from about 8% to-about 20%. :If a 100% "pickup apply these same percentages to the cloth. On the other hand, if say only a 50% pick-up is allowed andthesolu- 'tion applied'butonce, the impregnating solution .should contain the-material in'amountsvarying from 6% :'to.'40%

in order to=apply the material in the preferred amounts of 3% to 20%. In general applications, solution is usually applied but once withpickmps varying from 55% -to-100%.

The curing agent-added to the impregnating solution is an acid-acting material. Acid-acting as used herein is meant to include'acids as well as those materials not classified as acids but'which act as such. These agents include, among others, organic and inorganic a-cids'and their anhydride-s, such as citric acid, acetic acid, acetic: acid anhydride, butyric acid, caproic ac'id, phtha1ic acid,

phthalic .acid .anhydride, tartaric .acid, ,aconitic acid,

oxalic acid, succinic acid, succinicacid anhydride,.lactic acid, maleic acid, maleic acidanhydride, fumaric acid,

glutaconic acid, malonic acid, acetoacetic acid, n aphthalic..

acid, trimellitic acid, phosphoric acid, boric aid, sulfonic acid, perchloric acid, persulfuric-acid, and p-toluenesulfonic acid; metal salts,-such aszinc fluoborate, magnesium perchlorate, copper fluoborate, zinc y persulfate, zinc phosphate, ferrous perchlorate, nickelfluoborate, manganeses.

phosphate and strontium fluoborate; .and .aminehyd-rochlorides, such as-hydrochl-orides of aniline, benzylidene, .n-propylamine, di-. n-butyl amine, vdi.-benzylarnine, triethylamine, alpha-phenylethylamine, alpha-naphthylamine, :beta-aminoanthraquinone, 1,3-diamino-anthra-q -,quinone, piperidine, ,pyridine, .quinoline, vrnorpho'line,{pyr role andguanidine, and hydrochlorides. of hydroxyamines as .Z-amino-Z-methyl propanol and isobutanol amine.

Particularly preferred curing agents to be employed are the organic and .inorganic acids containing no moreithang 12 carbon ,atoms, the .salts of .metalshaving anatomic weight between 24 and 210 and inorganic acidthe anion :portion ofwhichcontains. at leasttwo dissimilar elements :havingan atomic weightaboveZ, suchas, forexample, oxalic acid, icitric acid, .succinic acid, zincv fluoborate,

copper perchlorate, magnesium perchlorate, barium per sulfate, iron perchlorate, and the like.

Coming underspecial consideration, particularly fbecaused the excellenLcolor-and exceptionally finecrease proofing,propertiesobtained therewith, are-the salts of metals of groups I to IV and VIII of the periodic ,table' of elements and inorganic acid the anion portion of which contains at least two dissimilar elements having an atomic weight above 2, and particularly inorganic acids of the formula wherein Xisa non-metal having an atomic weight above 2, Z'is an element which t'ends'to gain'from'1'to2 elecf trons in its: outer orbit, such "as oxygen and -fluorine,'m/-is an interger, y is an integer greater than 1, and a equals the valency of the radical (X)w(Z)y. such as sulfuric acid,

fluobor-ic acid, fluosilicic -acid, 'persulfuric acid, phosgphoric acid and the like.

ployed inamounts varying from about 0.5 to 20%, the .metal salts are preferablyemployed in-amounts varying from about 1% to ,-15%,-and;the amine hydrochlorides are preferably employed inamounts varyingfrom about 1% to%.

The solution-employed in the treatment of the textile fabrics according to the process. ofxthe invention may a lso derivatives. oftpolyhy'dricgalcohols, such as mono-,diand ;tr.i-acetin andiproductsobtained by condensing polyhydric alcohols with themselves or wtih aldehydes or ketones. The compositionsmay also containnatural resins,.e. g., shellac, and other natural resins and synthetic or semisynthetic resins e. .-g., .ester gum, polyhydroxy-polybasic acid resins, phenol aldehyde and 1 urea-aldehyde resins.

Textile softening agents may .also'be added in varying amounts to improve the feel.of the treated fabrics. Examples of .theseagents include, among others, pentadecyl -phenol,.octadecyl suocinic acid, octadecenyl sucoinic acid, sulfonated .waxes and, :sulfonated alcohols, dimerized long-chain unsaturated acids, non-ionic fatty acidesters of higher polyglycerols. Preferred softeners are the epoxidizeddiand triglycerides.

Theapplic'ation of the aqueous solution containing the polyep'oxides and polyaldehydes to the textile fabric may :bezeifectedin any suitable'man-ner, the method selected .depending'tupondhe results desired. If it is desired to ,applyrthetsolution' only5to one surface of'the material, as, .forrexample, whenit is desired totreat the back only of a fabric havinga face of-artificial or natural silk and a cotton back, the application may *be effected by spraying or'by means of rollers,;'orthe composition maybe spread Huponithe :surfaceiby means of a doctor blade. When, ?lrowever,:it is "desired 'to coat both surfaces of the material,

or if the material is to be thoroughlyimpregn-ated with it, the fabrici-maybewsimply dipped in the solution or run through oonventional type:padding rollers. The solutions may also be applied locally to the material, for example,

by meanszof printing: rollers :or by stencilling.

The .amountrofsthe.mixtureof polyexpoxide and polyaldehyde to be deposited onthe fabric will vary over a .wide range dependingt-u-pon'the degree of wrinkle resistance and shrink 'resistance desiredin the finished material. =If-the fabric is to'have a soft feehsuch as that intended iforuse 'forcdresses,.=shirts, 'etc'., the amount of mixture deposited will: generally vary from 3% to 20% by weight of the fabric. If stiiferma'terials are required such as *for.-the shoe fabrics,.draperies and the like, still higher .amounts of the:rnixture, such-as of the order of 25% to bykweightimay bedeposited.

If thedesiredamountof mixture of-polyepoxide and polyaldehydedeposited in'thefabric is not obtained in one application, the solutioncan be applied again or as many times as desired in order to brin-g the amountof the mixture up to the desired level.

Afterthe desired ,amountof. solution hasbeen applied to the'fabric,, the treated fabric is preferably dried for a short period to, remove some or..all of the dispersing liquid, such as water, and the like. This is generally accomplished by exposing thewetsheets to hot gas either slack or framed to dimension at temperatures ranging up to C. The period of drying will depend largely on the amountvof pick-up permitted during the application of the -solution,,and the concentration of the mixture of polyepoxide and polyaldehyde. In most instances, the dryingrperiods of from 1 to 30 minutes should be sufficient.

The dried fabric is then exposed torelatively high temperatures to-acceleratecure. Temperatures used for this ,purpose generally.-range;from 100.C.- to 200"- C., and more preferablyfrom 'C. to C. At these preferred temperature ranges the cure can 'gener'ally'be accomplished in from 1 to 10 minutes. Exposures of less than 3 minutes, e. g., 1 minute, may probably be used in continuous, commercial processing.

The process of the invention may be applied to the treatment of any textile fabric, colored or white. Such materials include the natural or artificial textile materials, such as cotton, linen, natural silk and artificial silk, such as the artificial silk obtained from cellulse acetate or other organic esters or et-hers of cellulose and the regenerated cellulosic type of artificial silk obtained by the viscose, cuprammonium or nitrocellulose process, jute, hemp, rayon, animal fibers, such as wool, hair, mohair, synthetic fibers including the fibers from polyesters, such as for example the ethylene glycolterephthalic acid polyesters (Dacron), the acrylic polyvinyls, such as for example the acrylonitrile polymers (Orlon), the polyethylenes, polyurethans (Perluran), polyvinyl alcohol proteins (Caslen), Alginic (Alginate rayon), non-acrylic polyvinyls as vinyl chloride and vinylidene polymers (Vinyon), mineral fibers (Fiberglas) polyamides, such as the aliphatic dicarboxylic acid-polyamides reaction products (Nylon). While the invention has been particularly described with relation to the treatment of woven fabrics, it may also be applied to other materials, for example, knitted or netted fabrics.

The materials treated according to the process of the invention will have excellent crease resistance and improved dimensional stability and may be used for a wide variety of important applications. The woven cotton, rayon and wool fabrics, both colored and white, contain ing conventional amounts of resin, e. g., from 3% to 25% by weight, may be used, for example, in the preparation of soft goods, such as dresses, shirts, coats, sheets, and the like, while the fabrics containing much larger amounts of the resin, e. g., 25% to 50% may be used in other applications demanding more crispness and fullness such as the preparation of rugs, carpets, drapes, upholsteries, shoe fabrics, and the like.

To illustrate the manner in which the invention may be carried out, the following examples are given. It is to be understood, however, that the examples are for the purpose of illustration and the invention is not to be regarded as limited to any of the specific materials or conditions recited therein.

The wrinkle recovery values reported in some of the examples were determined by the Monsanto Recovery Method. The tests were carried out at 65% relative humidity and 70 F. The shrink resistance was determined by following method: The treated cloth was washed in an automatic washer using 10 parts of concentrated ammonia and 10 parts of an alkylarylpolyether alcohol (Triton X-100) for 6 minutes at 160 F. After washing, the cloth was rinsed and tumble dried for 3 minutes in a drier. The cloth was then ironed with a flat bed press without tension. The change in length of the cloth before and after this procedure was reported as the shrinkage value.

EXAMPLE I (a) This example illustrates the unexpected improvement in both wrinkle resistance and shrink resistance that is obtained by using a combination of a polyepoxide and polyaldehyde on the treatment of rayon.

50 parts of Polyether A described above was combined with parts of polyethylene oxide condensation product of sorbitan monopalmitate and 50 parts of a 5% solution of polyvinyl alcohol and the mixture thoroughly stirred. 100 parts of alpha-hydroxyadipaldehyde and 7.5 parts of magnesium perchlorate were then stirred into the above mixture and sufficient water added to bring the total to 1000 parts (giving a 15% solution of polyepoxide and polyaldehyde).

Rayon cloth was then impregnated with the abovedescribed solution by means of a Butterworth-3-Roll laboratory padder. The cloth was then dried at 60 C.

TABLE NO. 1

Monsanto wrinkle Shrinkage Tensile Treating agent recovery (percent) strength (avg. warp lbs./m.

and fill) Mixture of polyether A and hydroxyadipaldehyde..- 162 0. 8 59 None (control) 3. 8-4. 2 60 (b) The above results are surprising and far better than could be expected by using the same amount of the Polyether A or alpha-hydroxy-adipaldehyde by themselves. This is shown by the following experiment.

Solution A was prepared as follows: 150 parts of Polyether A was combined with 7.5 parts of a polyethylene oxide condensation product of sorbitan monopalmitate and 50 parts of a 5% solution of polyvinyl alcohol and the mixture thoroughly stirred. 7.5 parts of magnesium perchlorate was then stirred into the above mixture and sufficient water added to bring the total to 1000 parts.

Solution B was prepared as follows: 150 parts of alpha-hydroxy-adipaldehyde was combined with 7.5 parts of a polyethylene oxide condensation product of sorbitan monopalmitate and 50 parts of a 5% solution of polyvinyl alcohol and the mixture stirred. 7.5 parts of magnesium perchlorate was then stirred into the above mixture and sutficient water added to bring the total to 1000 parts.

Strips of rayon cloth were then impregnated with each of the above solutions by means of a Butterworth-3-Roll laboratory padder. The strips were then dried at 60 C. for 5 minutes and cured at 160 C. for 5 minutes. The finished products were then washed and rinsed three times in warm water to remove any soluble material.

The wrinkle recovery (average warp and fill) and shrink resistance of the strips are shown in the table below.

TABLE NO. 2.

Monsanto wrinkle recovery (avg. warp and Shrinkage Treating agent (percent) Solution A Solution B From the above figures, it would be expected that the mixture of 50 parts of Polyether A and parts of alpha-hydroxyadipaldehyde as used in (a) above would give only a Wrinkle recovery value of about and a shrink resistance of 0.45, While it actually gave a wrinkle recovery of 162 and a shrink resistance of 0.3.

EXAMPLE II ability and nochlorine retention. The wrinkl'efrecovery value was 149 as compared to an expected value of about 145.

EXAMPLE III Example I (a) Wasrepeated with'the exception that the mixture employed as the crease and shrink proofing agent was made up of 75 parts of Polyether Aand 75 parts of alpha-hydroxyadipaldehyde. Theresultingimpregnated rayon cloth-had excellent crease and shrink resistance with littleloss'o'f tensile strength. In addition,

- parts of alpha-hydroxyadipaldehyde. The treatedcloth had the sameiproperties asthe cloth shownl in the preceding example.

EXAMPLE :V

This example illustrates the :unexpected improvement in wrinkle recovery and shrink resistance thatis obtained by using a combination of Polyether A and glyoxal with rayon.

100 partsof Polyether A was combined with .5 parts of a polyethylene oxide condensation product of sorbitan monopalrnitate and '50.parts of a solution of polyvinyl alcohol and the mixture thoroughly stirred. 50 parts of glyoxal and 7.5 parts of magnesium perchlorate were stirred into the above and water added to bring the total to 1000 parts.

Rayon cloth was then impregnated with the abovedescribed solution by means of a Butterworth-3-Roll laboratory padder. The cloth was then dried at 60 C. for 5 minutes and cured at 160 C. for 5 minutes. The finished product was washed and rinsed three times in warm water to remove any soluble material.

The cloth treated in the above-described manner had excellent wrinkle resistance and shrink resistance and were obtained with little loss of tensile strength. In addition, the cloth had a soft feel, good abrasion resistance, good color and good washability. The wrinkle recovery was 152 as compared to an expected 146.

EXAMPLE VII This example illustrates the improvement in wrinkle recovery and shrink resistance that is obtained by using a combination of Polyether A and succinaldehyde with rayon.

About 100 parts of Polyether A and 50 parts of succinaldehyde are mixed with an acidic solution containing 540 parts of Water, .25 part Methocel, 1.8 parts of a copolymer of vinyl methyl ether and maleic anhydride and .5 part of polyglycol fatty acid ester, and as the curing agent 7.5 parts of zinc fluoborate.

Rayon cloth is then impregnated with the above-described solution by means of a Butterworth-B-Roll laboratory padder. The cloth is then dried at 60 C. for 5 minutes and cured at 160 C. for 5 minutes. The finished product is then washed and rinsed three times in warm water to remove any soluble material.

The cloth treated in the above-described manner has excellent wrinkle resistance and shrink resistance and both are obtained with little loss of tensile strength. In addition, the cloth has a soft feel, good abrasion resistance, good color and good washability and no chlorine retention.

EXAMPLE VIII This example illustrates the unexpected improvement in wrinkle recovery and shrink resistance that is obtained by using a combination of Polyether B and alpha, gammadirnethyl alpha (allyloxymethyl) glutaraldehyde with rayon.

tained with little loss of tensile strength.

"14 About parts ofPolyether B described aboveand 75 parts of alpha,gam'rna-dimethyl-alpha-(allyloxymethyl) glutaraldehyde are mixed with an acidic solution containing 540 parts of water, .25 part Methocel, 1.8 parts of a copolymer of vinyl methyl ether and maleic anhydride and .5 part of polygly'col fatty acid ester, and asthe 'curing agent 5 parts of citric acid.

-Rayon cloth is then impregnated with the abovedescribed solution by means of a Butterworth-3-Roll laboratory padder. The cloth is then dried at 60 C. for 5 minutes and cured at C. for 5 minutes. The finished product is then .washed and rinsed threetimes in warm water to remove any soluble material.

Thecloth treated in the above-described manner has excellent'wrinkle and shrink resistance and both are ob- In addition, the cloth has a softfeel, good color and goodabrasion resistance.

Treated cloth havin'g rela'ted properties is obtained by replacingthe Polyether -B in the above-describediprocess withequal amounts of Polyether'C.

EXAMPLE IX This example illustrates the treatment of rayon with a mixture of Polyether D and alpha-hydroxyadipaldehyde.

About 50 parts 'ofPolyether D and IOOparts of 'alpha- 'hydroxy adipaldehyde are'mixed with 50 parts of a polyethylene oxide condensation product of sorbitan mono- ;pa'lmitate andSO-parts ofpolyvinyl alcohol and the'mixture slowly stirred together. 7.5 parts of zinc'fiuoborate is stirred into the mixture and then water is added-to b'ringthetotalup to 1000 parts.

Rayon cloth is then impragnated with'the'above-described solution by means of a Butterworth-3-Roll laboratory padder. The cloth is then dried at 60 C. for 5 minutes and cured at 160 C. for 5 minutes. The finished product is then washed and rinsed three times in warm water to remove any soluble material.

The cloth treated in the above-described manner has excellent wrinkle resistance and shrink resistance and both are obtained with little loss of tensile strength. In addition, the cloth has a soft feel, good abrasion resistance, good color and good washability and no chlorine retention.

EXAMPLE X Examples I (a) and II to VII are repeated with the exception that the impregnating solutions are applied to cotton. The sheets of cloth treated in this manner have the same color as before the treatment, have a soft feel, good crease and shrink resistance, good washability and no chlorine retention.

We claim as our invention:

'1. A process for rendering cellulosic textile fabrics crease and shrink resistant which comprises impregnating the cellulosic fabric with an aqueous solution containing a mixture of polyepoxide and an aliphatic polyaldehyde containing from 2 to 4 free groups and a minor quantity of an acid-acting curing agent, and heating the resulting impregnated fabric to a relatively high temperature for a short period.

2. A process as in claim I wherein the fabric is rayon.

3. A process as in claim 1 wherein the fabric is cotton.

4. A process as in claim 1 wherein the acidic catalyst is a salt of (1) a metal having an atomic weight between 24 and 210, and (2) an inorganic acid the anion portion of which contains at least two dissimilar elements having an atomic weight above 2.

5. A process for rendering cellulosic textile fabrics more crease and shrink resistant which comprises impregnating the cellulosic fabric with an aqueous solution containing a mixture of (1) a glycidyl polyether of a 75 polyhydric alcohol having an epoxy equivalency between 15 1.1 and 3 and a molecular weight between 170 and 800, and (2) an aliphatic polyaldehyde containing from 2 to 4 groups and from .1% to 30% by Weight of an acid-acting curing catalyst, and heating the resulting impregnated fabric to a temperature above 100 C. for a short period.

6. A process as in claim 5 wherein the catalyst is citric acid.

7. A process as in claim 6 wherein the catalyst is zinc fluoborate.

8. A process as in claim 6 wherein the catalyst is magnesium perchlorate.

9. A process as in claim 5 wherein the catalyst is a salt of (1) a metal of the group consisting of metals of groups I to IV and VIII of the periodic table of elements and (2) an inorganic acid of the formula wherein X is a non-metal having an atomic weight above 2, Z is an element which tends to gain from 1 to 2 electrons in the outer orbit, w is an integer, y is an integer greater than one, and a is equal to the valency of the radical (X)1.U(Z)y.

10. A process as in claim 5 wherein the polyepoxide is a glycidyl polyether of glycerol and the polyaldehyde is alpha-hydroxy-adipaldehyde.

11. A process as in claim 5 wherein the polyepoxide is a glycidyl polyether of glycerol and the polyaldehyde is glyoxal.

12. A process as in claim 5 wherein the polyaldehyde is succinaldehyde.

13. A process as in claim 5 wherein the polyaldehyde is an alpha,gamrna-dialkyl-alpha-(alkoxymethyl) glutaraldehyde.

14. A process as in claim 5 wherein the mixture of polyepoxide and polyaldehyde contains from 20% to by weight of polyepoxide and the remainder is polyaldehyde.

15. A process for rendering cellulosic textile fabrics more crease and shrink resistant which comprises impregnating the cellulosic fabric with an aqueous medium containing a mixture of (1) a polyepoxide consisting of a glycidyl polyether of a polyhydric phenol wherein the polyepoxide has an epoxy equivalency greater than 1.0 and a molecular weight above 200, and (2) an aliphatic dialdehyde having from 2 to 4 aldehyde groups and not more than 15 carbon atoms, and an acid-acting catalyst, and heating the resulting fabric to a temperature above C.

16. A textile fabric prepared by the process of claim 1.

17. A textile fabric prepared by the process of claim 5.

18. A textile fabric prepared by the process of claim 15.

References Cited in the file of this patent UNITED STATES PATENTS 2,441,859 Weisberg May 18, 1948 2,512,996 Bixler June 27, 1950 2,541,027 Bradley Feb. 13, 1951 2,606,810 Erickson Aug. 12, 1952 FOREIGN PATENTS 1,058,002 France Nov. 4, 1953 

1. A PROCESS FOR RENDERING CELLULOSIC TEXTILE FABRICS CREASE AND SHRINK RESISTANT WHICH COMPRISES IMPREGNATING THE CELLULOSIC FABRIC WITH AN AQUEOUS SOLUTION CONTAINING A MIXTURE OF POLYEPOXIDE AND AN ALIPHATIC POLYALDEHYDE CONTAINING FROM 2 TO 4 FREE 